Explosive Materials
v2.0.1 / 01 oct 05 / greg goebel / public domain
* This chapter provides basic definitions and concepts in explosive technology, and
describes the major types of explosive materials.
[1.1] DEFINITIONS
* Formally speaking, the subject of explosives, incendiaries, fireworks, and the like are
lumped under the term of "pyrotechnics", meaning "the science of fire". Actual usage of
these terms is more inconsistent, irregular, and confusing. It is easiest to describe them by
example:
The term "explosives" means chemical materials to create an explosion. Explosive
materials are used as "bursting charges" for bombs, missile warheads, grenades,
and mines, and as "propellants" to fire bullets and artillery shells. They are used
as "blasting charges" in military or commercial demolition, for earth-moving for
engineering projects, and demolition of buildings and other structures.
Explosives are categorized as "low" or "high" explosives. In low or "deflagrating"
explosives, such as black powder, the explosion propagates through the material at
subsonic speed through an accelerated burning or "combustion" process. In high
explosives, such as TNT, the explosion propagates by a supersonic "detonation", driven
by the breakdown of the molecular structure of the material. An explosive can be
characterized by the amount of energy it releases when detonated, as well as by its
shearing and shock effect, or "brisage".
Most modern high explosives are "stable" or "insensitive", meaning they are difficult to
set off by accident. A high-explosive charge generally needs an easily-activated
"detonator" or "blasting cap" to cause it to explode, and sometimes may also need a
secondary "booster charge" of intermediate sensitivity that is triggered by the detonator to
initiate the full explosion. Propellants equivalently need a "primer" and sometimes a
secondary "ignition charge" to set them off.
The term "incendiaries" means materials intended to start large-scale fires. The
best known incendiary material is "napalm" or jellied gasoline.
The terms "pyrotechnics", though in principle applicable to explosives and
incendiaries, is used in practice to label the grab-bag of other materials to create
small-scale fires, light, heat, noise, or gas emission. Pyrotechnic devices include
matches; flares; smoke grenades; airbag inflators; solid rockets; fuel pellets for
field stoves and other heating units; and quick-release devices used for emergency
exit systems in aircraft, or for staging or shroud ejection systems in space launch
vehicles.
The term "fireworks" means in practice any sort of explosive, incendiary, or
pyrotechnic device intended for use in entertainment. Fireworks include
firecrackers, skyrockets, smoke pots, whistlers, shells, and Roman candles.
Soldiers will of course occasionally light off grenades, shells, rockets and so on
strictly for entertainment value, but that doesn't really make them fireworks as
such.
[1.2] BASIC PRINCIPLES
* Most pyrotechnics and low explosives operate by combustion processes, in which a fuel
combines with oxygen to release heat, light, smoke, or gas. In such materials, a "fuel"
component is mixed with an "oxidizing" component that releases oxygen when heated,
since combustion rates would be limited if the fuel had to rely on the oxygen in the
atmosphere for combustion. For example, the fuel in black powder is charcoal and sulfur,
while the oxidizer is saltpeter, or potassium nitrate (KNO3). The reaction is:
2KNO3 + S -> K2S + 3CO2 + N2
The packaging of a pyrotechnic mixture affects its behavior. Confinement greatly speeds
up the combustion process by concentrating heat and hot gas in the reaction. In fact,
black powder will generally simply burn instead of explode unless packed into an
appropriate casing, such as the thick paper shell of a firecracker.
Burning rate is also increased by the homogeneity of the mixture: fine powders burn
faster than coarse grains. Liquid explosives are unsafe because they are extremely
homogenous; their mixing is at the molecular level, and so they can be set off by a mild
physical shock. Liquid explosives also tend to settle and separate in storage, changing
their chemical properties, and not generally for the better. Adding abrasives to an
explosive material makes it more sensitive, while adding lubricants like wax makes it
more stable. Materials that reduce explosive sensitivity are known as "stabilizers" or
"moderators".
Most high explosives operate by a chemical breakdown in their molecular structure, not a
combustion process between fuel and oxidizer. For example, nitroglycerine has the
molecular formula C3N3H5O9. Any small disturbance, such as heat or physical shock,
causes it to decompose into carbon dioxide (CO2), water (H2O), nitrogen (N2), and a
little excess oxygen (O2). This process still involves oxidation reactions, but the oxygen
is part of the molecule. During the breakdown of nitroglycerine, nitrogen-oxygen atomic
bonds are replaced by far more stable carbon-oxygen, hydrogen-oxygen, and nitrogen-
nitrogen bonds, with the process accompanied by a violent release of energy.
* Flares and fireworks are generally designed to emit light. Pyrotechnic materials emit
light by two processes, incandescence and line emission:
Incandescence, or "blackbody radiation", occurs when solid or liquid particles are
heated, causing them to emit a broad spectrum of radiation. The higher the
temperature, the higher the peak frequency of the emission, and as a particle
grows hotter it will glow red, orange, yellow, white, and finally blue. The total
energy output of an incandescent particle is also proportional to the fourth power
of the temperature, which means that making the combustion twice as hot makes
it sixteen times as bright.
Line emission, in contrast, occurs in a hot gas, and produces light through changes
in internal electron levels, with the light emitted only at specific frequencies
characteristic of the type of atom or molecule making up the gas. If the light
frequencies occur in the visible range, they will correspond to fairly pure colors.
Explosives, incendiaries, pyrotechnic devices, and fireworks can be ignited by flame,
friction, impact, electrical shock, high ambient temperatures, or even a laser beam. In
general, high explosives are designed to be insensitive. They can't be set off by a flame or
spark, and have to be set off by a shock from a detonator.
Certain "pyrotechnic" metals, such as magnesium, aluminum, zirconium, and uranium,
ignite at very high temperatures and burn very hot, releasing large amounts of energy. For
this reason, aluminum powder is sometimes added to explosives to enhance blast effect,
and magnesium is used to build bright flares. Incidentally, solid aluminum doesn't burn
well, since combustion builds up an oxide layer that resists further combustion.
[1.3] LOW EXPLOSIVES: BLACK POWDER
* While people have devised fiery and smoke-making materials for most of recorded
history, the first explosive material worthy of the name was black powder, developed by
the Chinese sometime in the first millennium AD. The Chinese used it to make
firecrackers and rockets for public entertainments, and also for a wide range of weapons.
Traditionally it was claimed that the Chinese didn't use it in warfare, but in fact they built
devices such as arrow projectors, "fire arrows" and "fire spears", bombs, mines, and
crude cannon.
Black powder migrated to the West in the Middle Ages. The English monk Roger Bacon
was one of the first Westerners to mention the material, in a letter written in 1267.
Tradition has it that Bacon was thought to have written a formula for black powder in
1242, using a code because of the deadly nature of the material, but this story appears to
be a myth, as does the story that it was introduced by a German monk named Berthold
Schwartz. Nobody really knows how black powder got to Europe, only that it was in use
there around the year 1300. The fact that the formula for it was obtained from China is
very difficult to dispute: early European formulations closely matched those of mature
Chinese formulations, which had been evolved over many years of trial-and-error
tinkering and actually included some minor useless components that were also copied in
European formulations.
In the 14th century, black powder led to the development of new weapons. In weapons,
black powder was used as a bursting agent and a propellant. Black powder charges were
used as "petards", or mines, to break down the walls of fortifications, and later as filler in
explosive shells and hand grenades. As a propellant explosive, black powder was used to
fire balls from muskets, as well as stones from primitive cannon called "bombards",
which eventually evolved into muzzle-loading artillery. Black powder became god of
war, and remained so until the last decades of the 19th century.
Engineers and miners were slow to adopt black powder. The earliest mentions of its use
in engineering projects go back to the middle of the 16th century and it didn't really
become widespread in commercial uses until the middle of the 17th century. Bofors
Industries, established in Sweden in 1646, was a pioneer in the manufacture of
commercial black powder. The reason that black powder was not in commercial use for
so long was because it had generally been expensive, mostly due to the cost of refining
saltpeter, and miners in particular were also unsurprisingly cautious about setting off
explosions underground. It was also not trivial to figure out how to properly drill holes
and pack explosives. One of the first major engineering projects performed with black
powder was a 156 meter (512 foot) canal tunnel blasted through a hill near Beziers,
France, in the 1690s. Black powder also became a standard tool for miners until the late
19th century.
* Early Chinese mixtures of black powder consisted of equal weights of charcoal, sulfur,
and saltpeter. Saltpeter is a shiny white crystalline material that could be found on the
walls of bat caves or in well-aged manure piles; today it is known to be potassium nitrate
(KNO3) and calcium nitrate (CaNO3). It is produced by bacteria that feed off organic
waste. Eventually, the formula for black powder was refined to a mix of charcoal, sulfur,
and saltpeter in the proportions 15:10:75 by weight. Oddly, other forms of carbon cannot
be substituted for charcoal. Charcoal inherits a latticelike structure from the wood from
which it was created, and is also laced with by-products of its partial combustion.
Charcoal and sulfur were relatively easy to obtain. Saltpeter was not too hard to obtain in
southeast China, where the hot and alternating wet / dry climate encouraged its creation
on manure piles, but it was much more troublesome to find in cool and damp Northern
Europe. Producing saltpeter was an obnoxious business. Manure was collected and stored
in a covered pit that was periodically "watered" with urine and turned over. The urine of
wine-drinkers was favored, since it helped encourage the growth of the bacteria that
generated the saltpeter, though at the time of course nobody knew exactly why it helped
produce more saltpeter. After a year or so, the waste was "refined" to extract the saltpeter.
It seems plausible that most people who worked in the business didn't have much social
contact with those who didn't.
At first, there was no way to separate the calcium nitrate from the potassium nitrate. Both
worked about as well as an oxidizer, but calcium nitrate absorbs water more easily than
potassium nitrate, or in other terms calcium nitrate is more "hygroscopic". The ground-up
charcoal in the powder was also hygroscopic, but calcium nitrate made matters much
worse, and powder made with it tended to go damp and "spoil" much more easily.
Eventually, schemes were developed by trial and error to refine out the calcium nitrate.
When the three ingredients were obtained, they were then finely ground together with a
mortar and pestle. This was a risky business, since it generated a fine, highly combustible
dust that could easily lead to explosions. Eventually urine or watered-down wine was
mixed in during grinding to help reduce the chance of explosions, though there was no
way to eliminate it completely.
Dampening the mix also helped in other ways. Early on, gunners using black powder had
to be very careful how they fluffed the fine powder into their weapons. If it was packed in
tightly, it would burn at the surface, just like a rocket, but not explode. To explode, it had
to be spooned in loosely and with an airspace left over. Since the saltpeter provided
oxygen to support the explosion, the airspace wasn't to admit oxygen, but to allow fire to
propagate quickly through the charge. Dampened black powder was pressed into balls or
loaves and dried, with the blocks of powder smashed down into grains before combat.
Such "corned" powder was introduced early in the 15th century and could be packed in
with much less care than fine powder and still explode easily, since the grain structure
gave plenty of space for the propagation of fire.
By the 19th century, the production of black powder had become an efficient industrial
process. Elements of a powder mill were separated from one another and set up in
buildings with three sturdy walls, plus a fourth thin wall and a thin roof that would direct
the blast of an accident away from the other buildings. Production of charcoal was
performed according to careful methods to generate the best possible product, and
industrial chemistry came up with less noxious and more industrially efficient means of
producing potassium nitrate.
Powder was ground under heavy mill wheel stones, and dampened with distilled water to
inhibit explosions. The final product was squeezed under heavy pressure into a block
with the hardness of slate, known as "presscake"; the denser powder packed more of a
punch. The presscake was broken up into grains, with the grains sifted into grades by
size, and then tumbled in barrels to give them a graphite "glaze" that kept the powder
from agglomerating in storage. A special form of industrial blasting powder was invented
that used cheap calcium nitrate instead of expensive potassium nitrate, with the grains
heavily glazed to prevent them from soaking up water.
* Black powder is an excellent explosive in many respects. Its raw materials are cheap,
abundant, nontoxic, and environmentally safe. It is stable, being indifferent to shock, and
can be stored indefinitely if kept dry. It can be easily ignited with a spark or fuze, though
this is by no means entirely a virtue. Black powder also has a number of limitations:
As noted, it has to be kept dry since it absorbs water, and so can be troublesome
to handle on naval vessels, or in military operations in wet weather.
It has limited explosive yield. Large quantities of it have to be used to obtain any
serious effect, and its low brisage meant it left much to be desired for use in
mining, quarrying, and earth-moving.
Its explosive properties are somewhat unpredictable. Sometimes black powder
lights off quickly and sometimes not, increasing the hazards of its use.
It burns dirty, creating a lot of smoke and fouling weapons after a few firings.
Battlefields in the days of black powder were covered with clouds of dirty smoke.
Although the first repeater firearms used black powder as a propellant, the
cumulative fouling of the barrel limited the effectiveness of such weapons.
Better explosives were needed and were developed, beginning in the middle of the 19th
century. However, the low cost and good properties of black powder make it still the
material of choice for fireworks, as will be discussed in the next chapter.
[1.4] COMMERCIAL HIGH EXPLOSIVES
* In 1846, an an Italian chemist named Ascanio Sobrero added glycerol to a mixture of
nitric and sulfuric acids, setting off an explosion that nearly killed him. He had
discovered the first high explosive. Sobrero to no surprise decided that the liquid he
called "nitroglycerine", now known to have the chemical formula C3H5O3(NO2)3, was
dangerous. He gave up his investigations of the material and did not publicize his work.
A Swedish chemical manufacturer named Immanuel Nobel began to produce
nitroglycerine for rock blasting in 1863. The process involved mixing glycerol with nitric
and sulfuric acids in several steps, using ice water as a coolant. Nitroglycerine can't be
detonated by a simple cord fuze -- a match can be thrown into a batch of it and it won't go
off -- but it is sensitive to shock, exactly the reverse of black powder. In 1865 Immanuel's
son Alfred Nobel devised the first detonator, a blasting cap consisting of a small charge
of fulminate of mercury (discussed below) with a cord fuze, to set it off. Nobel's
detonator was a significant step forward in the development of modern explosives
technology.
Nitroglycerine is a liquid explosive and dangerously touchy. In fact, it was so unsafe that
it is astounding in hindsight that anybody wanted to use it, and Nobel's brother Emile was
killed while working with it. It was often carelessly shipped as normal freight, without
markings to indicate special handling, and terrible accidents occurred. Nitroglycerine was
banned in several nations. Late in the 1860s, workers found that nitroglycerine that had
been frozen was almost impossible to detonate, and so manufacturers began to freeze it
for shipment. However, this was clearly a stopgap solution.
Alfred Nobel was already working on ways to make a safer explosive. He determined
that nitroglycerine was much less sensitive if it was absorbed in "diatomaceous earth", a
porous clay that consisted of the deposits of the skeletons of tiny sea creatures laid down
aeons before. This material could be packed into cardboard tubes and reliably
transported, handled, and detonated. It could not be set off by a spark or a flame. It was
not only safer than nitroglycerine, it was even safer than black powder. Nobel named it
"dynamite", and it quickly became the industrial explosive of choice.
Dynamite offered much of the power of nitroglycerine with greatly improved safety.
However, it was not perfect. The nitroglycerine in dynamite tends to "sweat out" in
storage, and even form puddles in crates. Cold weather also tends to crystallize the
nitroglycerine inside a stick of dynamite, making it more sensitive. Another problem is
that nitroglycerine causes dilation of blood vessels. Since it can be absorbed through the
skin, people who handle dynamite often have pounding headaches. Incidentally, because
of its ability to dilate blood vessels, nitroglycerine is also used in small doses as a
medicine for people with heart conditions.
The tendency of dynamite to become sensitive in storage made it dangerous to stockpile,
and so military forces were not enthusiastic about it. In 1875, Nobel figured out how to
mix nitroglycerine and nitrocellulose to produce a "blasting gelatin" that was more stable
than dynamite, and could also be detonated underwater. Nitrocellulose explosives are
discussed in a later section of this chapter.
* Despite its limitations, dynamite remained the predominant commercial explosive until
the 1950s, when "ammonium nitrate" explosives were began to predominate. Ammonium
nitrate (AN, with the chemical formula NH4NO3) is useful as an explosive when mixed
with other combustible or explosive substances, and in fact Alfred Nobel adopted it as a
dynamite enhancer as far back as 1867. A mixture of ammonium nitrate and diesel fuel
known as "ammonium nitrate fuel oil (ANFO)" is now commonly used as an industrial
explosive. It is also well known to makers of home-brewed explosives.
The fuel oil in ANFO provides a source of energy, while the ammonium nitrate provides
oxygen for the fuel's combustion. However, the breakdown of ammonium nitrate itself
produces energy, giving ANFO a hefty explosive kick. ANFO is much cheaper and less
sensitive than dynamite, and does not give users headaches, at least not by simply laying
hands on it.
In principle, home-brewed ANFO is synthesized by mixing diesel fuel and ammonium
nitrate fertilizer together until the mix has he consistency of toothpaste. In practice, it's
not that simple. Commercial fertilizer doesn't have the explosive potential of bomb-
quality ammonium nitrate, for which distribution is carefully controlled, and a simple mix
of fertilizer and diesel just burns and melts instead of exploding. To actually make an
explosive out of fertilizer, aluminum, zinc, or potassium sulfate (K2SO4) have to be
added to the mix as boosters. The amount of additive is critical: if too little is added, the
mix won't explode, and if too much is added, it's liable to go off unpredictably.
Synthesizing ANFO is not a job for the inept.
The potential danger of toying with ammonium nitrate was thoroughly demonstrated on
16 April 1947. A French freighter loaded with ammonium nitrate fertilizer was docked at
Texas City, Texas, on the Gulf Coast. The ship caught on fire in the morning and
attracted a crowd of spectators along the shoreline, who believed they were a safe
distance away. In mid-morning the ship exploded, killing hundreds with the tremendous
blast, sending a tidal wave surging over the shoreline, and setting refineries on the
waterfront on fire. A second ship loaded with fertilizer exploded after midnight, but
emergency workers were given warning, evacuated the vicinity of the vessel, and only
two people were killed. Fires burned for six days after the disaster. Official casualty
estimates came to a total of 567, but many victims were burned to ashes or literally blown
to bits, and the official total is believed to be an underestimate.
There was another massive explosion of a freighter loaded with ammonium nitrate
fertilizer in the harbor of Brest in France on 28 July 1947. These disasters convinced the
authorities that handling of ammonium nitrate needed to be regulated more carefully.
Ammonium nitrate is also used as the basis for what are called "gelled slurry explosives
(GSX)", which are generally used in mining applications. A typical formulation is
ammonium nitrate and powdered aluminum mixed in light oil, with polystyrene powder
added as a gelling agent. This form a mudlike mixture that can be pumped out holes
drilled in hard rock, and has high brisage for shattering such rocks. Some sources claim
that GSX actually uses water instead of oil, but this seems a bit implausible since
ammonium nitrate explosives have to be protected from water.
* As a footnote to the topic of commercial explosives, coal miners work in an
environment full of flammable coal dust, making the use of any kind of true explosive
dangerous. As a substitute, they use a "blasting charge" that consists of a cylinder full of
liquified carbon dioxide and containing a heating element. The carbon dioxide expands
rapidly when the heating element is activated, and bursts the container, producing a blast
but no flames.
[1.5] MILITARY HIGH EXPLOSIVES
* As mentioned in the previous section, explosives like nitroglycerine, dynamite, and
ANFO are not very well suited to combat use, though they all have been used in battle to
an extent. Different explosives have been developed for the battlefield and are widely
used by military forces. Of course, military explosives are also used to an extent in
commercial applications, but they are relatively expensive, and ANFO remains the bulk
explosive of choice for civilian uses.
The ideal military explosive is powerful, easy to handle, can be stockpiled for long
periods of time in any climate, and hard to detonate except under precisely specified
conditions. It also has to be loaded into shells, bombs, and the like, and so has to be
meltable, so it can be poured into shells; or plastic, allowing it to be "extruded" into shells
like caulk from a tube; or insensitive enough to allow it to be packed safely into the shell
in bulk form.
Military explosives have been improved for over a century and are now thoroughly
refined. The first military high explosive to be put into service was "trinitrophenol" or
"picric acid", a yellow crystalline substance with the chemical formula C6H3O7N3,
which was first demonstrated by the French in 1885. The British used in under the trade
name of "Liddite". However, picric acid has a high melting point, making the process of
filling shells with it difficult; reacts with heavy metals to form toxic compounds; tends to
be corrosive; and is also inclined to be sensitive.
The Germans developed a second military explosive in this time frame, known as
"nitroguanidine", chemical formula CH4N4O2. It was used in World War I and to an
extent in World War II in mortar shells and the like, usually mixed with other explosives.
Another military high explosive, "trinitrophenylmethlnitramine" or "tetryl" was
introduced at nearly the same time. It was powerful but not all that stable, and was often
used in detonators and as a booster. All three of these explosives are now generally out of
service.
The first modern military explosive was "trinitrotoluene (TNT)", with the formula
C7H5N3O6. TNT was discovered in the 1860s, but was not adopted for military use until
the early 20th century. It was widely used by most of the combatants in World War I. It is
relatively insensitive, and can be melted at low temperature to allow it to be poured into
bombs and shells.
The British also used TNT during World War I, but after the war adopted a more
powerful explosive named "Research Department Explosive (RDX)". RDX, more
precisely known as "cyclotrimethylenetrinitramine" and sometimes called "cyclonite" or
"hexogen", was originally formulated in 1899. It has the formula C3H6N6O6. It has the
insensitivity of TNT but greater explosive yield.
TNT and RDX are still the most important military explosives. Other military explosives
include:
"Ammonium picrate" AKA "Explosive D". Ammonium picrate has slightly less
explosive yield than TNT, but is the least sensitive military explosive. It is often
used in high-velocity armor-piercing shells, since it can stand the intense shock of
firing without detonating immediately.
"Pentaerythritol tetranitrate (PETN)", with the formula C5H8N4O12. PETN is a
relatively sensitive explosive, and is often used as a booster, or in "detonating
cord (detcord)", a type of explosive line used as a detonator and for small-scale
demolition tasks.
"HMX" or "Octogen" is said to be about 75% more powerful than TNT. It was
developed during World War II and was introduced into service after the war.
* In practice, most military explosives are mixtures of these explosives and other
materials. For example:
Although ANFO is not generally suitable for military use, since it's troublesome
to store without drying out, mixtures of AN and TNT known as "amatols" were
used in both WWI and WWII as a means of stretching the supply of explosives.
The proportion of AN in the mix ranged from 50% to 80%. A mix of ANFO,
TNT, and powdered aluminum enhancer named "Minol" is still in use.
RDX and TNT are mixed with wax to produce "Composition B" AKA "cyclotol".
RDX, TNT, and aluminum powder are combined in "High Brissance Explosives
(HBX)" such as "HBX-1", "HBX-3", and "H-6". These formulations are more
powerful than TNT. HBX-3 has a high proportion of aluminum powder enhancer
for shock effect, and is used in underwater munitions such as depth charges. It
appears that HBX-3 is also known as "Torpex", though this may be a slightly
different formulation.
Other explosive mixtures include "Pentolite" AKA "Pentrolit", which is half
PETN and half TNT; "Picritol", which is a roughly half-and-half mix of picric
acid and TNT; "Tetrytol", which is a mix of 70% tetryl and 30% TNT; and
"Octol", which is a mix of 75% HMX and 25% TNT.
RDX is often mixed with wax or other "plasticizers" to make "plastic explosives".
RDX-based plastic explosives include "Composition A", "Composition C", and
the Czech-made "Sempex". Composition A is produced in several different
formulations with the designations "A-1" through "A-5", though A-4 and A-5 are
not widely used. Similarly, Composition C has the formulations "C-1" through
"C-4". C-4 is favored by the US Army for demolition charges, and filler in
grenades and land mines.
In the early 1950s the notion of plastic explosives was extended by the introduction of
"polymer bonded explosives (PBX)", in which crystals of explosive materials are
intimately bonded into a polymer matrix. A wide range of PBX materials have been
fabricated, with explosives such as HMX, PETN, and RDX incorporated into polymers
such as nylon, polyurethane, and teflon. More recent work focused on developing matrix
plastics that actually have explosive properties themselves, with such amusing names as
"polyAMMO" and "polyBAMO".
One particularly interesting new explosive is "octaninitrocubane". This experimental
material is derived from "cubane", a hydrocarbon built around a cubical arrangement of
carbon atoms that was synthesized in the 1960s. The cubical core of cubane makes it very
dense, almost twice as dense as gasoline. In the early 1980s, US Army researchers
realized if cubane could be modified into a high explosive, its high density would permit
faster propagation of breakdown reaction, leading to a more powerful explosive, as well
as a more compact one.
Octaninitrocubane consists of a cubic core of eight carbon atoms, with an N2O group
attached to each corner of the cube. Although octaninitrocubane is still be evaluated,
researchers believe that it may be twice as powerful as TNT and very stable, and that its
breakdown products will be non-toxic carbon and nitrogen compounds.
[1.6] DETONATORS & PROPELLANTS
* Detonators have traditionally been made from "fulminate of mercury". This is a salt of
of "fulminic acid (HCNO)", which is a dangerous and unstable liquid explosive, and has
the formulas of Hg(CNO)2. Apparently there are a series of metal fulminates, such as
silver fulminate, that are more powerful but are generally too unstable to be safely used.
Fulminate of mercury was first synthesized in the 17th century, but it not easy to handle
and did not come into widespread use until the early 19th century. It is highly unstable,
and mercury is a relatively expensive material, not to mention a toxic heavy metal. It was
never suitable for general use as an explosive and found its niche as a detonator material,
particularly for percussion firearms. Due to its drawbacks, it is now generally out of use.
In modern times, "lead azide", with the formula Pb(N3)2, is the preferred material for
detonators, being more stable if less powerful. It is a salt of "hydrazoic acid (HN3)".
There are a number of different azides, with "sodium azide (NaN3)" in widespread use
for inflating automotive airbags.
* Black powder had been the only propellant available for firearms and artillery until the
mid-19th century, when various chemists began to investigate treatments of paper, wood
pulp, and particularly cotton with nitric acid (HNO3). These experiments resulted in
"guncotton", which had promise as a propellant as it burned quickly and produced a large
amount of gas. However, early formulations of guncotton were unsafe to produce and
handle. It also burned too fast, and could cause firearms to blow up in the shooter's face.
In 1865, a British chemist named Sir Frederick Abel, working on the problem of
manufacturing guncotton for the British government, came up with a manufacturing
process that involved pulping the cellulose feedstock, boiling it, and washing it before
treatment. Further effort demonstrated that nitrocellulose explosives could be used
effectively and with reasonable safety. The first form of smokeless powder to gain
widespread acceptance was "Poudre B" or "B powder", synthesized in 1884 by a French
chemist named Paul Vielle.
In 1888, Alfred Nobel developed a smokeless powder name "ballistite", based on his
formulation for blasting gelatine. This led to another smokeless powder, based on a
mixture of guncotton, gelatinized nitroglycerine, and petroleum jelly, developed by
Frederick Abel and James Dewar in 1889. The material was drawn out in a cord and so
was named "cordite". Cordite was adopted by the British, who did not trust B powder,
and by World War I cordite was the dominant propellant.
* All such "smokeless" powders were based on nitrocellulose. Cellulose is a long-chain
biopolymer found in plants, and treatment with nitric acid replaced hydroxyl groups (OH)
on the chain with nitrate groups (NO3). The higher the percentage of hydroxyl groups
replaced, the more powerful and sensitive the powder became. Creating a reliable
smokeless powder required manipulating the percentage of nitrate groups through
processing, and adding the appropriate moderators and other useful elements.
Modern propellants are categorized as "single-base", "double-base", and "multi-base" or
"composite" powders:
Single-base powders such as cordite are mostly nitrocellulose. They burn cool and
cause little barrel wear.
Double-base powders are mixtures of nitroglycerine and nitrocellulose such as
ballistite, and burn hotter.
Composite powders are modern formulations that do not contain nitrocellulose or
nitroglycerine, instead using more modern propellants that burn cool but are as
powerful as double-base powder.
Firearms now generally use single-base or composite powders. Double-base powders
were used as a propellant for small solid-fuel rockets, but have been largely or
completely replaced by modern solid fuels, discussed in the next chapter. Smokeless
powders are not truly smokeless, but they burn much more cleanly than black powder.
Burning rate of smokeless powders, as with other explosives, can be controlled by
varying the size of the powder grains, with large grains burning more slowly. Grains can
also be perforated so they burn from the inside as well as out.
